Studies on Molecular Devices showing Redox Response

本研究计画旨在建构具有电致变色等电化学反应之有机氧化还原体系。为了实现这样的分子系统，采用了一种新的分子设计方式，其中（1）带电物种将通过形成具有大π共轭的强发色团而不是通过芳构化来稳定，以及（2）在电子转移期间应该发生剧烈的结构变化。这些条件与长期以来用于设计多级氧化还原系统的条件有很大不同。“动态氧化还原行为“是本工作的核心概念，因此氧化还原对被设计为在电子转移时经历可逆的C-C键形成和断裂。以二苯并TTF为原型，详细研究了其插入环烷烃环的衍生物及其三环骨架的异构体。本文研究的一些分子被证明是可逆的动态氧化还原体系。为了构建电致变色体系，设计了其他含三芳基甲烷染料骨架的分子。六芳基乙烷衍生物和双（三芳基甲烷）双阳离子之间的可逆相互转化被证明。

The research project is intended to construct the organic redox systems which exhibit the electrochemical response such as electrochromism. In order to realize such molecular systems a new way of molecular designing was adopted where (1) the charged species would be stabilized by formation of strong chromophores with large pi-conjugation but not by aromatization and (2) drastic structural changes should be occurred during the electron transfer. These conditions are quite different from what had been used to design the multi-stage redox systems for a long time. The "dynamic redox behavior"is the central concept in this work, thus the redox pairs were designed so as to undergo reversible C-C bond formation andcleavage upon electron transfer. Dibenzo-TTF derivatives inserted with a cycloalkane ring as well as their isomersof the tricyclic skeleton were studiedin detail as prototypes. Some molecules studies here were proven to be thereversible dynamic redox systems . In orderr to construct the electrochromic systems other molecules containing triarylmethane dye skeletons were designed. The reversible interconversion between hexaarylethane derivatives and bis (triarylmethane) dications was demonstrated .